UPKAR PRAKASHAN, AGRA–2

By

Dr. Hemant KulshresthaHead, Department of Chemistry

St. John’s CollegeAgra

Through Solved Problems(With Multiple Objective Questions and their Explanations)

&Prof. Ajay Taneja

Department of ChemistryDr. B. R. Ambedkar University

Agra

Revised & Enlarged Edition

© Authors & Publishers

Publishers

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ISBN : 978-81-7482-381-6

Code No. 1588

Printed at : UPKAR PRAKASHAN (Printing Unit) Bye-pass, AGRA

PREFACE

We are extremely delighted to present this Revised Edition of Chemical Scienceswhich will cover the total need of the student preparing for CSIR-UGC (NET)examination for selection of scholars for Junior Research Fellowship of CSIR andUGC and for determining the eligibility for Lectureship in the Colleges andUniversities of India.

Our major objective is also to develop confidence among the candidates who aretaking competitive examination in the field related to Chemical Sciences providingthem solved objective as well as short descriptive type questions which covers bothfundamental and practical aspects of the topic. This book is designed to satisfy thechallenging requirements of NET (CSIR-UGC), GATE, SET, ONGC, IARI, BARCand M. Phil., Ph.D. Entrance of Various Indian Universities.

The final form of this book is the outcome of an extensive survey of relatedliterature than our knowledge. We have tried to consult the best available sources ofinformation in respect to various topics discussed. We sincerely hope that the bookwill go a long way to satisfy the long felt need of students for a friendly book onChemistry.

We gratefully acknowledge the assistance and constructive comments of ourcolleagues and Research students during the preparation of this book especially to Dr.Jaiswar Gautam, Asst. Professor Department of Chemistry, Dr. B. R. AmbedkarUniversity, Agra and Mr. Ram Kumar, Asst. Professor Department of Chemisry, St.John’s College, Agra for assisting us at various stages of writing this book. Anysuggestions for improvement of the book are welcome and will be gratefullyacknowledged.

—Authors

CONTENTS

● Previous Years’ Solved Papers

PART ‘A’

General Aptitude 1–96

PART ‘B’ & ‘C’Inorganic Chemistry

1. Chemical Periodicity ......................................................................................... 3–17

2. Structure and Bonding ....................................................................................... 18–50

3. Concepts of Acids and Bases............................................................................. 51–68

4. Main Group Elements and their Compounds .................................................... 69–176

5. Chemistry of Transition Elements and Coordination Compounds ................... 177–262

6. Inner Transition Elements ................................................................................. 263–279

7. Organometallic Compounds .............................................................................. 280–324

8. Gases and Metal Clusters .................................................................................. 325–337

9. Analytical Chemistry ......................................................................................... 338–360

10. Bio-Inorganic Chemistry ................................................................................... 361–392

11. Spectroscopy...................................................................................................... 393–412

12. Nuclear Chemistry ............................................................................................. 413–440

Physical Chemistery1. Basic Principles of Quantum Mechanic ............................................................ 3–24

2 & 3. Approximate Methods of Quantum Mechanics : The Variation Methodand Perturbation Theory, Term Symbols Many Electron Systems .................. 25–38

4. Chemical Bonding in Diatomics : MO, VB Theories, Huckel Theory forConjugated II-Electron Systems ....................................................................... 39–54

5. Group Theoretical Representation, Symmetry and Quantum Mechanics....... 55–716. Molecular Spectroscopy.................................................................................... 72–1017. Chemical Thermodynamics .............................................................................. 102–1528. Statistical Thermodynamics .............................................................................. 153–1749. Electro Chemistry.............................................................................................. 175–204

( v )

10. Chemical Kinetics ............................................................................................. 205–25011. Colloids and Surfaces ....................................................................................... 251–27112. Solid State ......................................................................................................... 272–29013. Polymer Chemistry ........................................................................................... 291–30614. Data Analysis .................................................................................................... 307–320

Organic Chemistry1. IUPAC Nomenclature ....................................................................................... 3–18

2. Principle of Stereochemistry ............................................................................. 19–37

3. Aromaticity........................................................................................................ 38–51

4. Organic Reactive Intermediates......................................................................... 52–68

5. Mechanism of Organic Reactions..................................................................... 69–108

6. Selective Organic Name Reactions ................................................................... 109–179

7. Organic Transformations and Reagents ............................................................ 180–228

8. Concepts in Organic Synthesis ......................................................................... 229–241

9. Asymmetric Synthesis ....................................................................................... 242–259

10. Pericyclic Reactions .......................................................................................... 260–288

11. Heterocyclic Chemistry ..................................................................................... 289–307

12. Chemistry of Natural Products ......................................................................... 308–351

13. Spectroscopy...................................................................................................... 352–380

Interdisciplinary Topics1. Chemistry in Nanoscience and Technology ...................................................... 3–9

2. Catalysis and Green Chemistry ......................................................................... 10–18

3. Medicinal Chemistry ......................................................................................... 19–29

4. Supramolecular Chemistry ................................................................................ 30–36

5. Environmental Chemistry.................................................................................. 37–48

GENERAL INFORMATION

SCHEME OF EXAMINATIONTime : 3 Hrs. Max. Marks : 200

Single Paper Test having Multiple ChoiceQuestions (MCQs) is divided in three parts.

PART ‘A’This part shall carry 20 questions pertaining

to General aptitude with emphasis on logicalreasoning graphical analysis, analytical andnumerical ability, quantitative comparisons, seriesformation, puzzles etc. The candidates shall berequired to answer any 15 questions. Eachquestion shall be of two marks. The total marksallocated to this section shall be 30 out of 200.

PART ‘B’This part shall contain 50 Multiple Choice

Questions (MCQs) generally covering the topicsgiven in the syllabus. A candidate shall berequired to answer any 35 questions. Eachquestion shall be of two marks. The total marksallocated to this section shall be 70 out of 200.

PART ‘C’This part shall contain 75 questions that are

designed to test a candidate’s knowledge ofscientific concepts and/or application of thescientific concepts. The questions shall be ofanalytical nature where a candidate is expected toapply the scientific knowledge to arrive at thesolution to the given scientific problem. Acandidate shall be required to answer any 25questions. Each question shall be of four marks.The total marks allocated to this section shall be100 out of 200.

● There will be negative marking @25% foreach wrong answer.

● To enable the candidates to go through thequestions, the question paper booklet shall bedistributed 15 minutes before the scheduled

time of the exam. The Answer sheet shall bedistributed at the scheduled time of the exam.

SYLLABUSPART ‘A’

This part shall carry 20 questions pertainingto General aptitude with emphasis on logicalreasoning graphical analysis, analytical andnumerical ability, quantitative comparisons, seriesformation, puzzles etc. The candidates shall berequired to answer any 15 questions. Eachquestion shall be of two marks. The total marksallocated to this section shall be 30 out of 200.

COMMON SYLLABUS FORPART ‘B’ & ‘C’

Inorganic Chemistry1. Chemical periodicity.2. Structure and bonding in homo- and

heteronuclear molecules, including shapes ofmolecules (VSEPR Theory).

3. Concepts of acids and bases, Hard-Soft acidbase concept, Non-aqueous solvents.

4. Main group elements and their compounds :Allotropy, synthesis, structure and bonding,industrial importance of the compounds.

5. Transition elements and coordinationcompounds : Structure, bonding theories,spectral and magnetic properties, reactionmechanisms.

6. Inner transition elements : Spectral andmagnetic properties, redox chemistry,analytical applications.

7. Organometallic compounds : Synthesis,bonding and structure, and reactivity.Organometallics in homogeneous catalysis.

8. Cages and metal clusters.9. Analytical chemistry : Separation,

spectroscopic, electro- and thermoanalyticalmethods.

( vii )

10. Bioinorganic chemistry : Photosystems,porphyrins, metalloenzymes, oxygentransport, electron- transfer reactions;nitrogen fixation, metal complexes inmedicine.

11. Characterisation of inorganic compounds byIR, Raman, NMR, EPR, Mössbauer, UV-vis,NQR, MS, electron spectroscopy andmicroscopic techniques.

12. Nuclear chemistry : Nuclear reactions,fission and fusion, radio-analytical techniquesand activation analysis.

Physical Chemistry1. Basic principles of quantum mechanics :

Postulates; operator algebra; exactly-solvablesystems — particle-in-a-box, harmonicoscillator and the hydrogen atom, includingshapes of atomic orbitals; orbital and spinangular momenta; tunneling.

2. Approximate methods of quantummechanics : Variational principle; perturba-tion theory up to second order in energy;applications.

3. Atomic structure and spectroscopy; termsymbols; many-electron systems andantisymmetry principle.

4. Chemical bonding in diatomics; elementaryconcepts of MO and VB theories; Huckeltheory for conjugated π-electron systems.

5. Chemical applications of group theory;symmetry elements; point groups; charactertables; selection rules.

6. Molecular spectroscopy : Rotational andvibrational spectra of diatomic molecules;electronic spectra; IR and Raman activities –selection rules; basic principles of magneticresonance.

7. Chemical thermodynamics : Laws, stateand path functions and their applications;thermodynamic description of various typesof processes; Maxwell’s relations; spontaneityand equilibria; temperature and pressuredependence of thermodynamic quantities; LeChatelier principle; elementary description ofphase transitions; phase equilibria and phaserule; thermodynamics of ideal and non-idealgases, and solutions.

8. Statistical thermodynamics : Boltzmanndistribution; kinetic theory of gases; partition

functions and their relation to thermodynamicquantities – calculations for model systems.

9. Electrochemistry : Nernst equation, redoxsystems, electrochemical cells; DebyeHuckeltheory; electrolytic conductance –Kohlrausch’s law and its applications; ionicequilibria; conductometric and potentiometrictitrations.

10. Chemical kinetics : Empirical rate laws andtemperature dependence; complex reactions;steady state approximation; determination ofreaction mechanisms; collision and transitionstate theories of rate constants; unimolecularreactions; enzyme kinetics; salt effects;homogeneous catalysis; photochemicalreactions.

11. Colloids and surfaces : Stability andproperties of colloids; isotherms and surfacearea; heterogeneous catalysis.

12. Solid state : Crystal structures; Bragg’s lawand applications; band structure of solids.

13. Polymer chemistry : Molar masses; kineticsof polymerization.

14. Data analysis : Mean and standard deviation;absolute and relative errors; linear regression;covariance and correlation coefficient.

Organic Chemistry1. IUPAC nomenclature of organic molecules

including regio- and stereoisomers.

2. Principles of stereochemistry: Configura-tional and conformational isomerism inacyclic and cyclic compounds; stereo-genicity, stereoselectivity, enantioselectivity,diastereoselectivity and asymmetricinduction.

3. Aromaticity: Benzenoid and non-benzenoidcompounds – generation and reactions.

4. Organic reactive intermediates: Generation,stability and reactivity of carbocations,carbanions, free radicals, carbenes, benzynesand nitrenes.

5. Organic reaction mechanisms involvingaddition, elimination and substitutionreactions with electrophilic, nucleophilic orradical species. Determination of reactionpathways.

6. Common named reactions and rearrange-ments – applications in organic synthesis.

( viii )

7. Organic transformations and reagents :Functional group interconversion includingoxidations and reductions; common catalystsand reagents (organic, inorganic,organometallic and enzymatic). Chemo,regio and stereoselective transformations.

8. Concepts in organic synthesis : Retro-synthesis, disconnection, synthons, linearand convergent synthesis, umpolung ofreactivity and protecting groups.

9. Asymmetric synthesis : Chiral auxiliaries,methods of asymmetric induction –substrate,reagent and catalyst controlled reactions;determination of enantiomeric anddiastereomeric excess; enantio-discrim-ination. Resolution – optical and kinetic.

10. Pericyclic reactions : Electrocyclisation,cycloaddition, sigmatropic rearrangementsand other related concerted reactions.

Principles and applications of photochemicalreactions in organic chemistry.

11. Synthesis and reactivity of commonheterocyclic compounds containing one ortwo heteroatoms (O, N, S).

12. Chemistry of natural products :Carbohydrates, proteins and peptides, fattyacids, nucleic acids, terpenes, steroids andalkaloids. Biogenesis of terpenoids andalkaloids.

13. Structure determination of organiccompounds by IR, UV-Vis, 1H & 13C NMRand Mass spectroscopic techniques.

Interdisciplinary Topics1. Chemistry in nanoscience and technology.2. Catalysis and green chemistry.3. Medicinal chemistry.4. Supramolecular chemistry.5. Environmental chemistry.

CSIR-UGC-NET/JRF Exam., June 2016 Solved PaperChemical Sciences

PART A

1. It takes 2 hours for Tiwari and Deo to do ajob. Tiwari and Hari take 3 hours to do thesame job. Deo and Hari take 6 hours to do thesame job. Which of the following statementsis incorrect ?(A) Tiwari alone can do the job in 3 hours(B) Deo alone can do the job in 6 hours(C) Hari does not work at all(D) Hari is the fastest worker

2. Abdul travels thrice the distance Catherinetravels, which is also twice the distance thatBinoy travels. Catherine’s speed is 1/3 ofAbdul’s speed, which is also 1/2 of Binoy’sspeed. If they start at the same time then whoreaches first ?(A) Both Abdul and Catherine(B) Binoy(C) Catherine(D) All three together

3. For a certain regular solid : number of faces +number of vertices = number of edges + 2.For Three such distinct (not touching eachother) objects, what is the total value of faces+ vertices – edges ?(A) Two (B) Four(C) Six (D) Zero

4. What will be the next figure in the followingsequence ?

(A) (B)

(C) (D)

5. A, B, C, D are points on a circle with AB = 5cm, BC = 12 cm, AC = 13 cm and AD = 7 cm.Then, the closest approximation of CD is—(A) 9 cm (B) 10 cm(C) 11 cm (D) 14 cm

6. Choose the four digit number, in which theproduct of the first & fourth digits is 40 andthe product of the middle digits is 28. Thethousands digit is as much less than the unitdigit as the hundreds digit is less than the tensdigit—(A) 5478 (B) 5748(C) 8745 (D) 8475

7. Equilateral triangles are drawn one inside theother as shown. What is the ratio of the twoshaded areas ?

(A) 2 : 1 (B) √⎯ 3 : 4(C) 4 : 1 (D) 8 : 1

8. A frog hops and lands exactly 1 metre awayat a time. What is the least number of hopsrequired to reach a point 10 cm away ?(A) 1(B) 2(C) 3(D) It cannot travel such a distance

9. A train running at 36 km/h crosses a mark onthe platform in 8 sec and takes 20 sec to crossthe platform. What is the length of theplatform ?(A) 120 m (B) 280 m(C) 40 m (D) 160 m

2 | CSIR Chemical Sci. (J-16)

10. When a polynomial f(x) is divided by x – 5 orx – 3 or x – 2, it leaves a remainder of 1.Which of the following would be thepolynomial ?(A) x3 – 10x2 + 31x + 31(B) x3 – 10x2 + 31x – 29(C) x3 – 10x2 + 31x – 31(D) x3 – 10x2 + 31x + 29

11. Water is slowly dripping out of a tiny hole atthe bottom of a hollow metallic sphereinitially full of water. Ignoring the water thathas flowed away, the centre of mass of thesystem—(A) remains fixed at the centre of the sphere(B) moves down steadily as the amount of

water decreases(C) moves down for sometime but eventually

returns to the centre of the sphere(D) moves down until half of the water is lost

and then moves up

12. The diagram (not to scale) shows the top viewand cross section of a pond having a squareoutline and equal sized steps of 0·5 m widthand 0·1 m height. What will be the volume ofwater (in m3) in the pond when it iscompletely filled ?

(A) 40·0 (B) 29·4(C) 19·4 (D) 11·3

13. D is a point on AC in the following trianglesuch that ∠ADB = ∠ABC. Then BD (in cm)is—

(A) 8 (B) 6(C) 3 (D) 4

14. The function f ( x ) is plotted against x asshown. Extrapolate and find the value of thefunction at x = – 1.

(A) – 0·01 (B) – 0·1(C) 0·01 (D) 0·1

15. A notebook contains only hundred statementsas under :1. This notebook contains 1 false statement.2. This notebook contains 2 false statements.···99. This notebook contains 99 false

statements.100. This notebook contains 100 false

statements.Which of the statements is correct ?(A) 100th (B) 1st

(C) 99th (D) 2nd

16. A chocolate bar having m × n unit square tilesis given. Calculate the number of cuts neededto break it completely, without stacking, intoindividual tiles—(A) (m × n) (B) (m – 1) × (n – 1)(C) (m × n) – 1 (D) (m × n) + 1

17. A person paid income tax at the rate of R%for the first 2 lakhs, and at the rate of (R +10)% for income exceeding Rs. 2 lakhs. If thetotal tax paid is (R + 5)% of the annualincome, then what is the annual income ?(A) 2·5 lakhs (B) 3·0 lakhs(C) 4·0 lakhs (D) 5·0 lakhs

18. An experiment leads to the following set ofobservations of the variable ‘v’ at differenttimes ‘t’.t 0 1 2 3 4 5 6v 5 6.1 9.1 13.7 20.6 30.8 41.4

CSIR Chemical Sci. (J-16) | 3

Allowing for experimental errors, which ofthe following expressions best describes therelationship between t and v ?

(A) v ∝ t 2 (B) (v – 5) ∝ t

2

(C) v = 5t + t 2 (D) (v – 5) = (t + 5)2

19. The difference between the squares of theages (in complete years) of a father and hisson is 899. The age of the father when his sonwas born—

(A) cannot be ascertained due to inadequatedata

(B) is 27 years

(C) is 29 years

(D) is 31 years

20. A bicycle tube has a mean circumference of200 cm and a circular cross section ofdiameter 6 cm. What is the approximatevolume of water (in cc) required tocompletely fill the tube, assuming that it doesnot expand ?

(A) 600 π (B) 1200 π(C) 3600 π (D) 1800 π

PART B

21. Identify the species, those obey the 18electron rule, from the following—

1. 2.

3. 4.

(A) 1 and 2 (B) 2 and 3

(C) 3 and 4 (D) 1 and 4

22. The following transformation

is an example of—(A) oxidative addition(B) insertion(C) β-hydride elimination(D) reductive elimination

23. [NiIIL6]n+ or n – shows absorption bands at8500, 15400, and 26000 cm–1 whereas[NiIIL′′′′6]n+ or n–, at 10750, 17500 and 28200cm– 1. L and L′′′′ are respectively—(A) OH– and N3

–

(B) Cl– and I– (C) NCS– and RCO2

–

(D) H2O and NH3

24. The number of microstates present in 3F termis—(A) 3 (B) 21(C) 9 (D) 28

25. CpM [Cp is (η 5 -C5H5)] fragment isolobalwith a BH fragment is—(A) CpGe (B) CpMn(C) CpRu (D) CpCo

26. The number of metal-metal bonds is—[Co2Fe2(Co)11(μ4-PPh)2] is—

(A) 3 (B) 4

(C) 5 (D) 6

27. Correct combination for π and π* orbitals inB2 molecule is—

π π*

(A) Gerade Ungerade

(B) Ungerade Gerade

(C) Gerade Gerade

(D) Ungerade Ungerade

28. The correct shape of [TeF5]– ion on the basisof VSEPR theory is—

(A) Trigonal bipyramidal

(B) Square pyramidal

(C) Pentagonal planar

(D) See-saw

29. The numbers of P-S and P-P bonds in thecompound P4S3 are, are respectively—

(A) 6 and 3 (B) 4 and 3

(C) 3 and 6 (D) 6 and 2

4 | CSIR Chemical Sci. (J-16)

30. In the iodometric titration of sodium thiosul-fate (Na2S2O3) with acidic dichromatesolution, 25 mL of 0·1 M dichromate requires25 mL of ‘x’ M thiosulfate. The value of ‘x’is—(A) 0·2 (B) 0·1(C) 0·6 (D) 0·4

31. Decomposition temperature of CaCO3 inthermogravimetric analysis will be highest indynamic atmosphere of—(A) nitrogen(B) synthesis gas(C) 1 : 1 mixture of O2 and CO

(D) water gas

32. On two sequential electron capture, 56Ba131

will give—(A) 54Xe131 (B) 54Xe130

(C) 56Ce131 (D) 56Ce130

33. The compound which dissolves in POCl3 togive a solution with highest chloride ionconcentration, is—(A) Et3N (B) KCl

(C) FeCl3 (D) SbCl5

34. In the absence of bound globin chain, hemegroup on exposure to O2 gives the iron-oxygen species—

(A)

(B)

(C)

(D)

35. For monoionic complex [UO2(NO3)3]–, thecorrect coordination number and geometryrespectively, are—(A) 8 and hexagonal bipyramidal(B) 5 and square pyramidal(C) 8 and square antiprism(D) 5 and trigonal bipyramidal

36. Chelate effect is—(A) predominantly due to enthalpy change(B) predominantly due to entropy change

(C) independent of ring size(D) due to equal contribution of entropy and

enthalpy change

37. The major product formed in the followingreaction is—

(A)

(B)

(C)

(D)

38. The major product formed in the followingreaction is—

(A) (B)

(C) (D)

39. The major product formed in the followingreaction is—

(A)

(B)

CSIR Chemical Sci. (J-16) | 5

(C)

(D)

40. Among the following, the compound thatdisplays an IR band at 2150 cm– 1 is—

(A) (B)

(C) (D)

41. In the 1H NMR spectrum of myrtenal, the twomethyl groups are expected to display signalsat (chemical shift values (δ) in ppm)

(A) 1.35 (s, 3H) and 5.0 (s, 3H)

(B) 0.74 (s, 3H) and 1.33 (s, 3H)

(C) 1.22 (s, 6H)

(D) 0.70 (s, 6H)

42. Among the following, the compound(s) thatcan be classified as terpene derivative is(are)

A B C

(A) A and B (B) A only(C) B only (D) B and C

43. The frontier orbital interactions involved inthe formation of the carbocation intermediatein the reaction of isobutylene with HCl are—(A) π of olefin and σ* of HCl

(B) π of olefin and σ of HCl

(C) π* of olefin and σ* of HCl

(D) π* of olefin and σ of HCl

44. The major product formed in the followingreaction is—

(A)

(B)

(C)

(D)

45. In the UV-visible absorption spectrum of anα , β-unsaturated carbonyl compound, withincreasing solvent polarity—

(A) n-π* transitions undergo hypsochromicshift, π-π* undergo bathochromic shift

(B) n-π* transitions undergo bathochromicshift, π-π* undergo hypsochromic shift

(C) both n-π* and π-π* transitions undergobathochromic shift

(D) both n-π* and π-π* transitions undergohypsochromic shift

46. The major product formed in the followingreaction is—

6 | CSIR Chemical Sci. (J-16)

(A)

(B)

(C)

(D)

47. In the following compound, the stereo-chemical descriptor for Ha and Hb is—

(A) enantiotopic

(B) diasterotopic

(C) homotopic

(D) constitutionally heterotopic

48. The correct statement are about the reactionof X and Y with NaNH2 are—

1. X reacts faster than Y

2. Y reacts faster than X

3. X and Y behave as Lewis acids

4. X is stronger Bronsted acid than Y

(A) 1 and 3 (B) 1 and 4

(C) 2 and 3 (D) 2 and 4

49. The correct statements about conformations Xand Y of 2-butanone are—

1. X is more stable than Y2. Y is more stable than X3. Methly groups in X are anti4. Methyl groups in Y are gauche(A) 1 and 4 (B) 1 and 3(C) 2 and 3 (D) 1, 3 and 4

50. The correct order of the magnitude of ‘Avalues’ for the given substituents incyclohexane derivatives is—

(A) Ph > CN > Me (B) Me > Ph > CN(C) CN > Me > Ph (D) Ph > Me > CN

51. The correct order of pka values for thecompounds X, Y and Z is—

(A) X > Y > Z (B) Y > Z > X(C) Z > X > Y (D) Y > X > Z

52. The following transformation proceedsthrough two consecutive electrocyclicprocesses, which are—

(A) 4π conrotatory and 6π conrotatory(B) 4π disrotatory and 6π conrotatory(C) 4π conrotatory and 6π disrotatory(D) 4π disrotatory and 6π disrotatory

53. The simultaneous eigenfunctions of angularmomentum operators L2 and Lz are—

(A) all of 2s, 2px, 2py and 2pz orbitals

(B) only 2s, 2px and 2py orbitals

(C) only 2s and 2pz orbitals

(D) only 2pz orbital

CSIR-UGC NET/JRF/SET ChemicalSciences

Publisher : Upkar Prakashan ISBN : 9788174823816Author : Dr HemantKulshrestha And Dr AjayTaneja

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